CN105705427B

CN105705427B - Liquid package container

Info

Publication number: CN105705427B
Application number: CN201580002655.5A
Authority: CN
Inventors: 田中祐介; 城后洋祐; 野岛裕介; 大下晋弥
Original assignee: Kuraray Co Ltd
Current assignee: Kuraray Co Ltd
Priority date: 2014-04-09
Filing date: 2015-04-08
Publication date: 2017-06-06
Anticipated expiration: 2035-04-08
Also published as: ES2645653T3; JP2016155604A; US9655816B2; CA2929367A1; JP5886486B1; CA2929367C; CN105705427A; TW201542195A; TWI574684B; US20160287474A1; EP3053849A1; WO2015156334A1; EP3053849A4; JPWO2015156334A1; KR101713503B1; KR20160057497A; EP3053849B1

Abstract

Liquid package container is provided, it possesses broken bag intensity high and low internal layer adherence under more important improved flexibility for medicinal liquid packing container, the transparency, high heat-sealing strength, normal temperature and low temperature.Specifically, there is provided following liquid package container, it is made up of at least 3 layers with internal layer, intermediate layer and outer layer of layered product, and the internal layer is by following resin combinations（Y）Composition, the outer layer is by following resin combinations（Z）Composition, foregoing intermediate layer is by following resin combinations（X）Composition.Resin combination（X）：Polypropylene-based resin containing 100 mass parts（1）, the specific thermoplastic elastomer (TPE) of 5 ~ 95 mass parts（2）With the special ethylene alpha olefin copolymer of 10 ~ 95 mass parts（3）Resin combination.Resin combination（Y）：Polypropylene-based resin containing 100 mass parts（1'）With the specific thermoplastic elastomer (TPE) of 5 ~ 250 mass parts（2'）Resin combination（Wherein, without specific ethylene-alpha-olefin copolymer, even if or containing again smaller than 10 mass parts）.Resin combination（Z）：Polypropylene-based resin containing 100 mass parts（1''）With the specific thermoplastic elastomer (TPE) of 0 ~ 35 mass parts（2''）Resin combination.

Description

Liquid package container

Technical field

The present invention relates to liquid package container.

Background technology

As therapeutic medical liquid package container, such as infusion bag, it is possible to use glassware, plastic products etc..Injection To infusion bag liquid sealed after, generally using water vapour sterilizing, autoclave sterilize etc. method sterilized.Glassware ratio Plastic products weight, and there is a problem of easily because of conveying when impact, whereabouts etc. and breakage, therefore widely use plastic defeated Liquid bag.

As plastic infusion bag, it is possible to use the polyolefin such as flexible vinyl chloride resin, polyethylene or polypropylene Product.The resinous infusion bag of flexible vinyl chloride contains substantial amounts of plasticizer in order to assign flexibility, therefore, according to transfusion kind The difference of class, plasticizer is possible to dissolution into infusing, and query is enjoyed in terms of security.In addition, medical instruments are disposable , therefore, the resinous infusion bag of flexible vinyl chloride is also incinerated after use, has and produces having from flexible vinyl chloride resin The problem of poisonous gas.In addition, the infusion bag of the polyolefin such as polyethylene, polypropylene not plasticizer-containing, therefore be in terms of health Preferably, but flexibility is low and impact resistance is insufficient, therefore be can not be said to be in terms of treatability sufficient.

On the other hand, to improve flexibility, sealing and resistance to adhesive as problem, it is proposed that by polypropylene-based resin group Compound is used as sealant（Internal layer）Medical multilayer film, the polypropylene-based resin composition comprising 50 ~ 98 mass % crystallization The specific hydrogenated block copolymer of property polypropylene-based resin, the special ethylene-alpha olefin copolymer of 1 ~ 49 mass % and 1 ~ 49 mass % Thing（With reference to patent document 1）.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2009-149861 publications.

The content of the invention

The invention problem to be solved

Multilayer film described in patent document 1 discloses it and can be used for medical container.In the embodiment of patent document 1, ethene- The content of alpha olefin copolymer is adjusted to below 5 mass %, but found according to the further research of the present inventor etc. without exception： Using polypropylene-based resin composition of the content of ethene-alpha-olefin copolymer in the degree as the medical containers such as infusion bag During the material in intermediate layer, due to aftermentioned mechanism, liquid package container is easily damaged because of impact, whereabouts etc..

In addition, the medical containers such as infusion bag are made after by the way that multilayer film is overlapped to being sealed around it, therefore will Ask the heat seal strength of the internal layer to be contacted with transfusion high.On the other hand, it is necessary to evade internal layer to be adhered each other and be difficult to injection transfusion, Therefore, the selection of the inner layer material being combined with intermediate layer is also important.It should be noted that according to the present inventor's etc. Further study and find：The sealant used in the embodiment of patent document 1（Internal layer）Material occur internal layer adhesion wind Danger is high.

Thus, problem of the invention is, there is provided with more important good for medicinal liquid packing container Flexibility, the transparency, high heat-sealing strength, low temperature（Such as -10 DEG C ~ 10 DEG C or so）And normal temperature（Such as 15 DEG C ~ 30 DEG C or so）Under Broken bag intensity high and low internal layer adherence liquid package container.

The means used to solve the problem

The present inventor etc. has made intensive studies, and as a result finds：By using by with internal layer, intermediate layer and outer layer extremely Few 3 layers layered product is constituted and only intermediate layer includes aftermentioned specific resin composition（X）Liquid package container, can reduce in Layer adhesion, and can control because of impact, the method for generation of cracking for falling etc. and producing, as a result, can be in low temperature and normal temperature It is lower to obtain broken bag intensity high, above-mentioned problem is can solve the problem that, so as to complete the present invention.

The present invention relates to following [1] ~ [8].

[1] liquid package container, it is made up of at least 3 layers with internal layer, intermediate layer and outer layer of layered product, described Internal layer is by following resin combinations（Y）Composition, the outer layer is by following resin combinations（Z）Composition, foregoing intermediate layer is by following Resin combination（X）Composition.

Resin combination（X）：Polypropylene-based resin containing 100 mass parts（1）, 5 ~ 95 mass parts thermoplastic elastomer (TPE) （2）With the ethene-alpha-olefin copolymer of 10 ~ 95 mass parts（3）Resin combination, the polypropylene-based resin（1）In be derived from The content of the construction unit of propylene monomer is more than 60mol%；The thermoplastic elastomer (TPE)（2）Being will be with polymer blocks（A） And polymer blocks（B）Block copolymer hydrogenation obtained from thermoplastic elastomer (TPE), the polymer blocks（A）With from virtue The construction unit of race's vinyl compound is 2,500 ~ 100,000, aforementioned polymer block as main body and number-average molecular weight（B） Using the construction unit from conjugated diene compound as main body, the content of vinyl bonding structure unit as more than 50mol% and Number-average molecular weight is 10,000 ~ 300,000, the polymer blocks（B）More than the 80mol% of the carbon-to-carbon double bond having is carried out Hydrogenation, the thermoplastic elastomer (TPE)（2）Number-average molecular weight be 20,000 ~ 500,000, the ethene-alpha-olefin copolymer（3） In be derived from vinyl monomer construction unit content be 50 ~ 95mol%.

Resin combination（Y）：Polypropylene-based resin containing 100 mass parts（1’）With the thermoplastic elastomehc of 5 ~ 250 mass parts Gonosome（2’）Resin combination, the polypropylene-based resin（1’）In be derived from the content of construction unit of propylene monomer and be More than 60mol%, the thermoplastic elastomer (TPE)（2’）With using the construction unit from aromatic vinyl compound as main body Polymer blocks and using the construction unit from conjugated diene compound as the polymer blocks of main body, wherein, without active It is the ethene-alpha-olefin copolymer of 50 ~ 95mol% from the content of the construction unit of vinyl monomer, even if or containing again smaller than 10 Mass parts）.

Resin combination（Z）：Polypropylene-based resin containing 100 mass parts（1’’）With the thermoplastic elastomehc of 0 ~ 35 mass parts Gonosome（2’’）Resin combination, the polypropylene-based resin（1’’）In be derived from the content of construction unit of propylene monomer and be More than 60mol%, the thermoplastic elastomer (TPE)（2’’）With using the construction unit from aromatic vinyl compound as main body Polymer blocks and using the construction unit from conjugated diene compound as the polymer blocks of main body.

[2] according to the liquid package container of above-mentioned [1], wherein, foregoing ethene-alpha-olefin copolymer（3）In 230 DEG C, load Melt flow rate (MFR) under conditions of lotus 21.6N is 0.1 ~ 30g/10 minutes, and fusing point is 40 ~ 120 DEG C.

[3] according to above-mentioned [1] or the liquid package container of [2], wherein, aforementioned polypropylene system resin（1）、（1’）With （1’’）Be each independently selected from HOPP, Propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene- Butene random copolymer, propylene-ethylene-butene random copolymer, propylene pentene-1 random copolymer, butene-hexene random copolymerization In thing, propylene-octene random copolymer, propylene-ethylene-pentene random copolymer and propylene-ethylene-hexene random copolymer At least a kind.

[4] according to the liquid package container of any one of above-mentioned [1] ~ [3], wherein, aforementioned polypropylene system resin（1’）'s Fusing point is 120 ~ 140 DEG C.

[5] according to the liquid package container of any one of above-mentioned [1] ~ [4], wherein, aforementioned polypropylene system resin（1’’） It is HOPP.

[6] according to the liquid package container of any one of above-mentioned [1] ~ [5], wherein, aforementioned thermoplastic's elastomer（2’）With （2’’）Being each independently will be with polymer blocks（A）And polymer blocks（B）Block copolymer hydrogenation obtained from heat Thermoplastic elastic, the polymer blocks（A）Using the construction unit from aromatic vinyl compound as main body and number divide equally Son amount is 2,500 ~ 100,000, the polymer blocks（B）Using the construction unit from conjugated diene compound as main body, The content of vinyl bonding structure unit is more than 50mol% and number-average molecular weight is 10,000 ~ 300,000, and aforementioned polymer is embedding Section（B）In more than the 80mol% of carbon-to-carbon double bond that has be hydrogenated with, and the number-average molecular weight of the thermoplastic elastomer (TPE) is 20,000~500,000。

[7] according to the liquid package container of any one of above-mentioned [1] ~ [6], wherein, the thickness of abovementioned layers is in internal layer 5 ~ 30 μm, 100 ~ 300 μm of intermediate layer, the scope of 15 ~ 120 μm of outer layer.

[8] medical container, it has the liquid package container of any one of above-mentioned [1] ~ [7].

The effect of invention

In accordance with the invention it is possible to provide with good flexibility, the transparency, high heat-sealing strength, low temperature and normal temperature The liquid package container of broken bag intensity high and low internal layer adherence.By the way that with these characteristics, flexible package punch of the invention holds Device is used for medical application with being particularly suitable for.

Brief description of the drawings

Fig. 1 be the cracking ways of carrying out for showing the liquid package container in embodiment and comparative example look-out station and The ideograph of the ways of carrying out that is cracked.

Fig. 2 is the photo figure of scanning electron microscope when cracking ways of carrying out is observed in embodiment 1.

Fig. 3 is the photo figure of scanning electron microscope when cracking ways of carrying out is observed in comparative example 1.

Specific embodiment

In this specification, preferred restriction can arbitrarily select, and the preferred combination with one another that limits can be described as more preferably 's.

[liquid package container]

The present invention is liquid package container, and it is made up of at least 3 layers with internal layer, intermediate layer and outer layer of layered product, The internal layer is by following resin combinations（Y）Composition, the outer layer is by following resin combinations（Z）Composition, foregoing intermediate layer by Following resin combinations（X）Composition.

（Resin combination（X））

Polypropylene-based resin containing 100 mass parts（1）, 5 ~ 95 mass parts thermoplastic elastomer (TPE)（2）With 10 ~ 95 mass The ethene-alpha-olefin copolymer of part（3）Resin combination, the polypropylene-based resin（1）In be derived from propylene monomer structure The content of unit is more than 60mol%；The thermoplastic elastomer (TPE)（2）Being will be with polymer blocks（A）And polymer blocks （B）Block copolymer hydrogenation obtained from thermoplastic elastomer (TPE), the polymer blocks（A）With from aromatic vinyl chemical combination The construction unit of thing is 2,500 ~ 100000, the polymer blocks as main body and number-average molecular weight（B）With from conjugation two The construction unit of ene compound is more than 50mol% as main body, the content of vinyl bonding structure unit and number-average molecular weight is 10000 ~ 300000, aforementioned polymer block（B）More than the 80mol% of the carbon-to-carbon double bond having is hydrogenated with, the thermoplastic Property elastomer（2）Number-average molecular weight be 20000 ~ 500000；The ethene-alpha-olefin copolymer（3）In be derived from vinyl monomer Construction unit content be 50 ~ 95mol%.

（Resin combination（Y））

Polypropylene-based resin containing 100 mass parts（1’）With the thermoplastic elastomer (TPE) of 5 ~ 250 mass parts（2’）Resin Composition, the polypropylene-based resin（1’）In be derived from propylene monomer construction unit content be more than 60mol%, the heat Thermoplastic elastic（2’）With polymer blocks and Yi Yuan using the construction unit from aromatic vinyl compound as main body The construction unit of self-conjugate diolefin compound as main body polymer blocks（Wherein, the structure from vinyl monomer is not contained The content of unit is the ethene-alpha-olefin copolymer of 50 ~ 95mol%, even if or containing again smaller than 10 mass parts）.

（Resin combination（Z））

Polypropylene-based resin containing 100 mass parts（1’’）With the thermoplastic elastomer (TPE) of 0 ~ 35 mass parts（2’’）Resin Composition, the polypropylene-based resin（1’’）In be derived from propylene monomer construction unit content be more than 60mol%, the heat Thermoplastic elastic（2’’）With polymer blocks and Yi Yuan using the construction unit from aromatic vinyl compound as main body The construction unit of self-conjugate diolefin compound as main body polymer blocks.

Liquid package container has by aforementioned resin by between foregoing internal layer and foregoing outer layer（X）Composition Intermediate layer, thus as the broken bag intensity high having concurrently under good flexibility, the transparency, high heat-sealing strength, low temperature and normal temperature, with And the liquid package container of low internal layer adherence.

Hereinafter, first against the resin combination used in intermediate layer（X）Each composition be described in detail.

(polypropylene-based resin（1）〕

As resin combination（X）The middle polypropylene-based resin for using（1）If, the construction unit from propylene monomer Content（Hereinafter sometimes referred to simply as propylene content.）For more than 60mol% is just not particularly limited, it is possible to use known polypropylene It is resin.The content of the construction unit from propylene monomer be preferably more than 80mol%, more preferably 80 ~ 100mol%, further Preferably 90 ~ 100mol%, particularly preferably 95 ~ 99mol%.As the construction unit from the monomer beyond propylene monomer, remove For example originating from the construction unit of vinyl monomer, from 1- butylene, 1- hexenes, 1- heptene, 1- octenes, 4-methyl-1-pentene, 1- Outside the construction units of 'alpha '-olefin monomers such as nonene, 1- decene, construction unit from aftermentioned modifying agent etc. can be also included.

As polypropylene-based resin（1）, can include such as HOPP, Propylene-ethylene random copolymer, propylene- Ethylene block copolymer, propene-1-butene random copolymer, propylene-ethylene-butene random copolymer, propylene pentene-1 random copolymerization Thing, propylene-hexene random copolymer, propylene-octene random copolymer, propylene-ethylene-pentene random copolymer, propylene-second Alkene-hexene random copolymer and their modifier etc..As the modifier, can include：It is grafted to polypropylene-based resin Modifier obtained from copolymerizing modifier；Make modifier etc. obtained from main chain of the modifying agent copolymerization in polypropylene-based resin.Make It is the modifying agent, such as maleic acid, citraconic acid, halogenated maleic acids, itaconic acid, cis -4- cyclohexene -1,2- dicarboxyls can be included The unsaturated dicarboxylics such as sour, interior-cis-bicyclo [2.2.1] -5- heptene -2,3- dicarboxylic acids；The ester of unsaturated dicarboxylic, acid amides Or acid imide；Maleic anhydride, citraconic anhydride, halogenated maleic acids acid anhydride, itaconic anhydride, cis -4- cyclohexene -1,2- dicarboxylic anhydrides, The unsaturated dicarboxylic acid anhydrides such as interior-cis-bicyclo [2.2.1] -5- heptene -2,3- dicarboxylic anhydrides；Acrylic acid, methacrylic acid, bar The unsaturated monocarboxylics such as beans acid；The ester of unsaturated monocarboxylic（Methyl acrylate, ethyl acrylate, methyl methacrylate, methyl Ethyl acrylate etc.）, acid amides or acid imide etc..As polypropylene-based resin（1）, preferably it is not modified.

Wherein, from less expensive and from the viewpoint of can easily obtaining, preferably HOPP, propylene-ethylene without Rule copolymer, more preferably propylene-ethylene block copolymer, HOPP, Propylene-ethylene random copolymer, it is further excellent Elect Propylene-ethylene random copolymer as.

Polypropylene-based resin（1）Can be used singly or in combination of two or more.

From resin combination（X）Molding processibility from the viewpoint of, polypropylene-based resin（1）In 230 DEG C, 21.6N Under the conditions of determine melt flow rate (MFR)（MFR）Preferably 0.1 ~ 30g/10 minutes, more preferably 1 ~ 20g/10 minute, it is further Preferably 1 ~ 10g/10 minutes.It should be noted that " melt flow rate (MFR) " recorded in the specification and claims is It is the value determined according to JIS K 7210.

In addition, polypropylene-based resin（1）Fusing point be not particularly limited, preferably 120 ~ 180 DEG C, more preferably 120 ~ 170 DEG C, more preferably 140 ~ 170 DEG C.It should be noted that " fusing point " recorded in the specification and claims is It is the value of the method measure recorded using embodiment.

(specific thermoplastic elastomer (TPE)（2）〕

As resin combination（X）The middle specific thermoplastic elastomer (TPE) for using（2）, it is by with polymer blocks（A） And polymer blocks（B）Block copolymer hydrogenation obtained from thermoplastic elastomer (TPE), the polymer blocks（A）With from virtue The construction unit of race's vinyl compound is 2,500 ~ 100000, the polymer blocks as main body and number-average molecular weight（B） Using the construction unit from conjugated diene compound as main body, the content of vinyl bonding structure unit（Below it is sometimes referred to as It is vinyl bonds resultant.）For more than 50mol% and number-average molecular weight are 10000 ~ 300000, aforementioned polymer block（B）Have More than the 80mol% of carbon-to-carbon double bond be hydrogenated with, the number-average molecular weight of the thermoplastic elastomer (TPE) is 20000 ~ 500000.

Hereinafter, for polymer blocks（A）And polymer blocks（B）Illustrate successively.

（Polymer blocks（A））

Polymer blocks（A）Using the construction unit from aromatic vinyl compound as main body.Referred herein to " with * * As main body " refer to based on polymer blocks（A）Gross mass, comprising the matter of construction unit 50 from aromatic vinyl compound Amount more than %.From resin combination（X）The transparency and mechanical property from the viewpoint of, the polymer blocks（A）In be derived from aromatics The content of the construction unit of vinyl compound is based on polymer blocks（A）Gross mass be more preferably more than 70 mass %, enter one Step is preferably more than 90 mass %.

As above-mentioned aromatic vinyl compound, such as styrene, o-methyl styrene, a methylbenzene second can be included Alkene, p-methylstyrene, AMS, Beta-methyl styrene, 2,6- dimethyl styrenes, 2,4- dimethyl styrenes, Methyl styrene between Alpha-Methyl o-methyl styrene, Alpha-Methyl, Alpha-Methyl p-methylstyrene, Beta-methyl o-methyl styrene, Methyl styrene, Beta-methyl p-methylstyrene, 2,4,6- trimethyl styrenes, alpha-methyl-2,6- dimethyl benzenes between Beta-methyl Ethene, alpha-methyl-2,4- dimethyl styrenes, Beta-methyl -2,6- dimethyl styrenes, Beta-methyl -2,4- dimethyl styrenes, Chloro styrene, m-chlorostyrene, to chlorostyrene, 2,6- dichlorostyrenes, 2,4 dichloro benzene ethene, α-chlorine neighbour's chlorobenzene second Alkene, α-chlorine m-chlorostyrene, α-chlorine are to chlorostyrene, β-chlorine chloro styrene, β-chlorine m-chlorostyrene, β-chlorine to chlorobenzene second Alkene, 2,4,6- trichlorostyrenes, α-chloro- 2,6- dichlorostyrenes, α-chloro- 2,4 dichloro benzene ethene, β-chloro- 2,6- dichloro-benzenes second Alkene, β-chloro- 2,4 dichloro benzene ethene, o-tert-butyl styrene, a t-butyl styrene, p-tert-butylstyrene, O-methoxy Styrene, meta-methoxy styrene, to methoxy styrene, o-chloromethyl ethene, a 1-chloro-4-methyl-benzene, to chloromethylbenzene Ethene, O-bromo methyl styrene, a bromometllylstyrene, to bromometllylstyrene, by silicyl replace styrene derived Thing, indenes, vinyl naphthalene etc..Wherein, from from the viewpoint of the balance of manufacturing cost and physical property, preferably styrene, Alpha-Methyl benzene Ethene and their mixture, more preferably styrene.

Wherein, do not damaging in the range of the object of the invention and effect, polymer blocks（A）Can be containing from aromatics second The construction unit of other unsaturated monomers beyond alkenyl compound.As other unsaturated monomers, can include and for example select From butadiene, isoprene, 2,3- dimethyl -1,3- butadiene, 1,3- pentadienes, 1,3- hexadienes, isobutene, styrene, O-methyl styrene, a methyl styrene, p-methylstyrene, p-tert-butylstyrene, 2,4- dimethyl styrenes, vinyl Naphthalene, vinyl anthracene, methyl methacrylate, methyl vinyl ether, N- VCzs, nopinene, 8,9- are to menthene, diamyl At least a kind in alkene, methene norbornene, 2- methylene tetrahydrofurans etc..Polymer blocks（A）Other are derived from containing this not The speciation during construction unit of saturation monomer is not particularly limited, can be any one in random, taper.

Polymer blocks（A）Contain the construction unit from other unsaturated monomers beyond aromatic vinyl compound When, its content is based on polymer blocks（A）Gross mass be preferably below 10 mass %.

Polymer blocks（A）Number-average molecular weight for 2,500 ~ 100000, be preferably 2,500 ~ 50000, more preferably 3000~30000.It should be noted that " number-average molecular weight " recorded in the specification and claims is by gel It is impregnated with chromatogram（GPC）The number-average molecular weight of the polystyrene standard conversion for determining and obtaining, is according to embodiment more specifically The method of record and the value that determines.

In addition, from by resin combination（X）From the viewpoint of the caoutchouc elasticity and flexibility of the layer of formation, polymer blocks （A）Content be preferably 5 ~ 40 mass %, more preferably 7 ~ 35 mass %, more preferably 10 ~ 35 mass %, particularly preferably 10 ~ 27 mass %, most preferably 10 ~ 25 mass %.It should be noted that thermoplastic elastomer (TPE)（2）In polymer blocks（A）'s Content is to pass through¹The value that H-NMR spectrum is obtained, is the value of the method measure recorded according to embodiment more specifically.

（Polymer blocks（B））

Polymer blocks（B）Using the construction unit from conjugated diene compound as main body.Referred herein to " with * * make It is main body " refer to based on polymer blocks（B）Gross mass comprising from conjugated diene compound the mass % of construction unit 50 with On.The polymer blocks（B）In the construction unit from conjugated diene compound content be based on polymer blocks（B）It is total Quality is more preferably more than 70 mass %, more preferably more than 90 mass %.

As composition polymer blocks（B）Conjugated diene compound, can include and be selected from butadiene, isoamyl two At least a kind in alkene, 2,3- dimethyl -1,3- butadiene, 1,3- pentadienes, 1,3- hexadienes etc..Wherein, preferably fourth two The mixture of alkene, isoprene, butadiene and isoprene.

In addition, polymer blocks（B）By from two or more conjugated diene compound（Such as butadiene and isoprene）'s When construction unit is constituted, their speciation is not particularly limited, and can include random, taper, completely interaction, part block Shape, block or their combination of more than two kinds.

From resin combination（X）Flexibility from the viewpoint of, polymer blocks（B）Number-average molecular weight for 10000 ~ 300000th, be preferably 20000 ~ 270000, more preferably 40000 ~ 240000, more preferably 75000 ~ 240000, especially Preferably 85000 ~ 220000.

Polymer blocks（B）In, vinyl bonding structure unit（For example, being 1,2- keys in the case of divinylic monomer Construction unit is closed, for 1,2- bonding structure units are total with 3,4- bonding structure units in the case of isoprene monomer） Content be more than 50mol%.The content of vinyl bonding structure unit is preferably 50 ~ 90mol%, more preferably 50 ~ 80mol%.

It should be noted that from from the viewpoint of heat resistance and weatherability, polymer blocks（B）The carbon-to-carbon being had is double More than the 80mol% of key is hydrogenated with（Hereinafter sometimes referred to simply as hydrogenate.）, preferably more than 85mol% hydrogenated, more preferably More than 90mol% is hydrogenated.It should be noted that the value is referred to as into hydrogenation rate sometimes.The higher limit of hydrogenation rate is without special Limit, higher limit can be 99mol%, can be 98mol%, can be 95mol%.

It should be noted that above-mentioned hydrogenation rate is used before and after hydrogenation¹H-NMR spectrum is directed to polymer blocks（B） In the construction unit from conjugated diene compound in carbon-to-carbon double bond content and the value that calculates, more specifically, be according to Method that embodiment is recorded and the value that determines.

And then, do not damaging in the range of the purpose of the present invention and effect, polymer blocks（B）Can be conjugated containing being derived from The construction unit of other polymerizable monomers beyond diolefin compound.As other polymerizable monomers, example is preferably included Such as selected from styrene, AMS, o-methyl styrene, a methyl styrene, p-methylstyrene, to tert-butyl benzene second The aromatic vinyl compounds such as alkene, 2,4- dimethyl styrenes, vinyl naphthalene and vinyl anthracene and methyl methacrylate, first Base vinyl ethers, N- VCzs, nopinene, 8,9- are to menthene, cinene, methene norbornene, 2- methylene four At least a kind compound in hydrogen furans etc..Polymer blocks（B）Containing from other polymer beyond conjugated diene compound Monomer construction unit when, its speciation is not particularly limited, can be any one in random, taper.

Polymer blocks（B）During containing construction unit from other polymerizable monomers beyond conjugated diene compound, Its content is based on polymer blocks（B）Gross mass be preferably below 30 mass %, more preferably below 10 mass %.

（Polymer blocks（A）With polymer blocks（B）Bonding pattern）

Thermoplastic elastomer (TPE)（2）As long as polymer blocks（A）With polymer blocks（B）Bonding has been carried out then to be bonded it Form is not particularly limited, and can be the bonding that straight-chain, branched, radial or their two or more combinations are obtained Any one in mode.Wherein, polymer blocks（A）With polymer blocks（B）Bonding scheme be preferably straight-chain, as it Example, by polymer blocks（A）It is shown as A and by polymer blocks（B）When being shown as B, the three block shown in A-B-A can be included and be total to Five block copolymers shown in Tetrablock copolymer, A-B-A-B-A shown in polymers, A-B-A-B,（A-B）NX type copolymers（X Coupling agent residue is represented, n represents more than 3 integer）Deng.Wherein, from thermoplastic elastomer (TPE) ease of manufacturing, flexibility etc. Viewpoint is set out, and preferably uses triblock copolymer（A-B-A）.

Herein, in this specification, it is bonded to by the coupling agent etc. of two functions in polymer blocks of the same race linear When, the polymer blocks being bonded integrally are regarded as a polymer blocks.Thus, including it is above-mentioned be illustrated in, originally should be tight Lattice are expressed as Y-X-Y（X represents coupling residue）Polymer blocks except especially needs carry out area with single polymer blocks Y It is overall outside situation about dividing to be shown as Y.In this specification, this polymer blocks comprising coupling agent residue are located in as described above Reason, thus, for example A-B-X-B-A should be expressed as comprising coupling agent residue and closely（X represents coupling agent residue）Block Copolymer is expressed as A-B-A, is shown as one of triblock copolymer.

In addition, thermoplastic elastomer (TPE)（2）In, within the scope without prejudice to the object of the present invention, there may be polymer blocks （A）And polymer blocks（B）In addition, the polymer blocks comprising other polymerizable monomers（C）.Now, by polymer blocks （C）When being shown as C, as the structure of block copolymer, A-B-C types triblock copolymer, the block of A-B-C-A types four can be included and be total to Polymers, A-B-A-C type Tetrablock copolymers etc..

Thermoplastic elastomer (TPE)（2）Number-average molecular weight for 20000 ~ 500000, be preferably 35000 ~ 400000, more preferably 40000 ~ 300000, more preferably 40000 ~ 200000.Thermoplastic elastomer (TPE)（2）Number-average molecular weight be less than 20000 when, Resin combination（X）Heat resistance reduction, on the other hand, during more than 500000, resin combination（X）Molding processibility become It is insufficient.

In addition, thermoplastic elastomer (TPE)（2）Molecular weight distribution（Mw/Mn）It is not particularly limited, from gained resin combination Mechanical strength from the viewpoint of, preferably 1.0 ~ 1.4, more preferably 1.0 ~ 1.2, more preferably 1.00 ~ 1.10, it is optimal Elect 1.00 ~ 1.05 as.It should be noted that the molecular weight distribution（Mw/Mn）It is to be determined according to the method for embodiment record Value.

Thermoplastic elastomer (TPE)（2）In, do not damaging in the range of the purpose of the present invention and effect, can be in strand And/or molecular end have it is one kind or two or more in the functional groups such as carboxyl, hydroxyl, anhydride group, amino, epoxy radicals.

On thermoplastic elastomer (TPE)（2）Mobility, from improve resin combination（X）The viewpoint of molding processibility go out Hair, the melt flow rate (MFR) determined under 230 DEG C, 21.6N is preferably 0.1 ~ 80g/10 minutes, more preferably 5 ~ 50g/10 points Clock.

（Aforementioned thermoplastic's elastomer（2）Manufacture method）

Thermoplastic elastomer (TPE)（2）Can be manufactured by solution polymerization process, emulsion polymerization or solid phase polymerization method etc..Wherein, Preferably solution polymerization process, for example, can apply anionic polymerisation, cationic polymerization plasma polymerization, radical polymerization etc. Known method.Wherein, preferably anionic polymerization.In anionic polymerization, by solvent, anionic polymerization initiator In the presence of required lewis base, successively add aromatic vinyl compound, conjugated diene compound and obtain block be total to Polymers, is then hydrogenated with to block copolymer, it is hereby achieved that thermoplastic elastomer (TPE)（2）.

As the organo-lithium compound for being used as polymerization initiator in the above-mentioned methods, such as lithium methide, ethyl can be included List two lithium compounds such as lithium compound and the lithium of four ethene two such as lithium, amyl group lithium, n-BuLi, s-butyl lithium, tert-butyl lithium etc..

As solvent, as long as anionic polymerisation is not had undesirable effect just being not particularly limited, example can be included Such as hexamethylene, hexahydrotoluene, n-hexane, pentane aliphatic hydrocarbon；Aromatic hydrocarbons such as benzene,toluene,xylene etc..In addition, poly- Close reaction is generally carried out 0.5 ~ 50 hour at 0 ~ 100 DEG C.

Lewis base has the effect of the micro-structural in the construction unit of voltage input self-conjugate diolefin compound.As described Lewis base, can include for example dimethyl ether, Anaesthetie Ether, tetrahydrofuran, dioxs, ethylene glycol dimethyl ether, pyridine, N, N, N ', N '-tetramethylethylenediamine, Trimethylamine, N-methylmorpholine etc..Lewis base can be used alone, it is also possible to group Conjunction uses two or more.

After being polymerized by the above method, addition alcohols, carboxylic acids, water isoreactivity hydrogen compound and make polymerisation end Only, hydrogenated in the presence of a hydrogenation catalyst in not active organic solvent according to known method such that it is able to be made and add Hydrogen thing.As described above, in the present invention, using the aforementioned polymer block in aforesaid block copolymer（B）The carbon-to-carbon being had The product that more than the 80mol% of double bond is hydrogenated with.

Hydrogenation can in the presence of a hydrogenation catalyst in 20 ~ 100 DEG C of reaction temperature, 0.1 ~ 10MPa of Hydrogen Vapor Pressure Under conditions of carry out.

As hydrogenation catalyst, such as Raney's nickel can be included；Make platinum（Pt）, palladium（Pd）, ruthenium（Ru）, rhodium（Rh）, nickel （Ni）Deng Metal Supported obtained from the carriers such as carbon, aluminum oxide, diatomite uneven catalyst；By comprising the race of nickel, cobalt etc. the 8th The combination of the organo-aluminum compounds or organo-lithium compound etc. such as the organo-metallic compound and triethyl aluminum, triisobutyl aluminium of metal The Ziegler series catalysts of formation；By the double of the transition metal such as titanium, zirconium, hafnium（Cyclopentadiene）Compound and lithium, sodium, potassium, aluminium, zinc Or the metallocene series catalysts that are formed of the combination of the organo-metallic compound of magnesium etc. etc..

Thermoplastic elastomer (TPE) obtained from so operating（2）Can be obtained as below：Polymerization liquid is injected into methyl alcohol etc. And after solidifying it, heated or drying under reduced pressure, or polymerization liquid is injected into boiling water, implementation is gone by azeotropic After except the air lift of solvent, it is thermally dried or drying under reduced pressure.

(ethene-alpha-olefin copolymer（3）〕

As resin combination（X）The middle ethene-alpha-olefin copolymer for using（3）As long as, the knot from vinyl monomer The content of structure unit（Hereinafter sometimes referred to simply as ethylene contents.）For 50 ~ 95mol% is just not particularly limited, it is possible to use known Ethene-alpha-olefin copolymer.

As ethene-alpha-olefin copolymer（3）, such as ethylene-propylene copolymer, ethene -1- butenes can be included Thing, ethene -1- hexene copolymers, ethene -1- heptene copolymers, ethylene-l-octane copolymer, ethene -4-methyl-1-pentene are common Polymers, ethene -1- nonenes copolymer, ethene -1- decene copolymers etc., their modifier etc..As the modifier, can enumerate Go out to these modifiers obtained from copolymer grafted copolymerizing modifier, modifying agent copolymerization is obtained in the main chain of these copolymers Modifier for arriving etc..As modifying agent, such as maleic acid, citraconic acid, halogenated maleic acids, itaconic acid, cis -4- rings can be included The unsaturated dicarboxylics such as hexene -1,2- dicarboxylic acids, interior-cis-bicyclo [2.2.1] -5- heptene -2,3- dicarboxylic acids；Unsaturated two The ester of carboxylic acid, acid amides or acid imide；Maleic anhydride, citraconic anhydride, halogenated maleic acids acid anhydride, itaconic anhydride, cis -4- cyclohexene - The unsaturated dicarboxylic acid anhydrides such as 1,2- dicarboxylic anhydrides, interior-cis-bicyclo [2.2.1] -5- heptene -2,3- dicarboxylic anhydrides；Acrylic acid, The unsaturated monocarboxylics such as methacrylic acid, crotonic acid；The ester of unsaturated monocarboxylic（Methyl acrylate, ethyl acrylate, methyl-prop E pioic acid methyl ester, EMA etc.）, acid amides or acid imide etc..As ethene-alpha-olefin copolymer（3）, preferably do not carry out It is modified.

Wherein, from less expensive and from the viewpoint of can easily obtaining, preferably ethylene-propylene copolymer, ethene -1- Butylene copolymer, ethylene-l-octane copolymer.

From resin combination（X）Molding processibility from the viewpoint of, ethene-alpha-olefin copolymer（3）In 230 DEG C, load Melt flow rate (MFR) under conditions of lotus 21.6N be preferably 0.1 ~ 30g/10 minutes, more preferably 1 ~ 20g/10 minute, it is further Preferably 1 ~ 10g/10 minutes.

In addition, ethene-alpha-olefin copolymer（3）Fusing point be not particularly limited, preferably 40 ~ 120 DEG C, more preferably 40 ~ 105 DEG C, more preferably 40 ~ 70 DEG C.

Ethene-alpha-olefin copolymer（3）Can be used singly or in combination of two or more.

（The content of each composition）

Resin combination（X）Contain polypropylene-based resin（1）（Hereinafter referred to as composition（1））100 mass parts, thermoplastic elastic Body（2）（Hereinafter referred to as composition（2））5 ~ 95 mass parts and ethene-alpha-olefin copolymer（3）（Hereinafter referred to as composition（3））10~ 95 mass parts.

Relative to composition（1）100 mass parts, composition（2）Content when being less than 5 mass parts, flexibility and transparent step-down, During more than 95 mass parts, molding processibility deteriorates, therefore economy is deteriorated.From from the viewpoint of identical, resin combination（X）In Composition（2）Content relative to composition（1）100 mass parts are preferably 10 ~ 95 mass parts, more preferably 10 ~ 90 mass parts, enter One step is preferably 15 ~ 85 mass parts, is most preferably 20 ~ 85 mass parts.

In addition, composition（3）Content relative to composition（1）When 100 mass parts are less than 10 mass parts, the broken bag under normal temperature is strong Degree will not improve.Research according to the present inventor etc. and specify that：The reason for causing such case is as follows.The heat-sealing of internal layer Position can turn into by the caused damaged starting point such as impact, whereabouts with the line of demarcation of non-heat-seal land.Tortoise is produced by the line of demarcation Split, in composition（3）Content relative to composition（1）100 mass parts less than in the case of 10 mass parts, enter by the cracking in such as Fig. 1 Like that, cracking is carried out line mode B towards the surface of liquid package container, therefore cannot obtain sufficient broken bag intensity.It is another Aspect specify that：If composition（3）Content relative to composition（1）100 mass parts are more than 10 mass parts, then such as the tortoise in Fig. 1 Split ways of carrying out A like that, first produce cracking, cracking to stop in the intermediate layer to surface direction towards the surface of liquid package container Extend, thereafter, cracking is carried out along internal layer with the interface in intermediate layer, as a result, liquid package container can be avoided damaged and nothing Method is used, and broken bag intensity is improved.The real original of the travel direction of cracking is controlled or induces ways of carrying out A as being cracked Because being still not clear, but it is presumed as follows.In other words, the resin combination in intermediate layer is constituted（X）In, composition（1）With composition（2）Phase Capacitive is high, therefore as homogeneous phase, it turns into continuous phase.Speculate：By making wherein to contain more than ormal weight and composition（1）'s The composition of compatibility shortcoming（3）, composition（3）In composition（1）It is middle dispersion and form dispersed phase, the dispersed phase is orientated, be cracked Dispersed phase is pursued along interface growth.Generally for soft and uniform intermediate layer is made, the composition of compatibility is short of（3）'s Content is few or does not contain composition（3）, but in the present invention, by increasing composition on the contrary（3）Content and be found that new effects.

On the other hand, composition（3）Content relative to composition（1）When 100 mass parts are more than 95 mass parts, flexibility and thoroughly Bright property reduction.

From from the viewpoint of identical, resin combination（X）In composition（3）Content relative to composition（1）100 mass parts Preferably 10 ~ 70 mass parts, more preferably 10 ~ 55 mass parts, more preferably 10 ~ 40 mass parts, particularly preferably 10 ~ 35 Mass parts.

(other compositions)

Resin combination（X）In, except aforesaid ingredients（1）~（3）Outside, do not damaging in the range of effect of the present invention, can To contain the additives such as antioxidant, ultra-violet absorber, light stabilizer, colouring agent, crystallization nucleating agent；Hydrogenation coumarone indene The hydrogenation such as resin, hydrogenated rosin system resin, hydrogenated terpene resin, alicyclic ring family hydrogenated petroleum resin is resin；By alkene and two The resin of tackification such as the fatty family resin that olefin polymer is formed；Hydrogenated polyisoprene, hydrogenated butadiene polymer, hydrogenation of benzene second Alkene-butadiene random copolymer, hydrogenated styrene isoprene random copolymer, butyl rubber, polyisobutene, polybutene etc. Other polymer.

It should be noted that resin combination（X）In, from from the viewpoint of effect of the invention, aforesaid ingredients（1）~（3） Total content be preferably more than 50 mass %, more preferably more than 70 mass %, more preferably more than 80 mass %, more preferably 90 More than quality %, more preferably more than 95 mass %.

（Internal layer）

Then, illustrated for the layer contacted with the liquid i.e. material of internal layer.Internal layer is by following resin combinations（Y）Group Into.

Resin combination（Y）：Polypropylene-based resin containing 100 mass parts（1’）With the thermoplastic elastomehc of 5 ~ 250 mass parts Gonosome（2’）Resin combination, the polypropylene-based resin（1’）In be derived from the content of construction unit of propylene monomer and be More than 60mol%, the thermoplastic elastomer (TPE)（2’）With using the construction unit from aromatic vinyl compound as main body Polymer blocks and using the construction unit from conjugated diene compound as the polymer blocks of main body（Wherein, without active It is the ethene-alpha-olefin copolymer of 50 ~ 95mol% from the content of the construction unit of vinyl monomer, even if or containing again smaller than 10 Mass parts）.

Herein, described in qualifications " be derived from vinyl monomer construction unit content for 50 ~ 95mol% ethene- Alpha olefin copolymer " is equivalent to aforementioned resin（X）Composition（3）.Contain aforementioned polypropylene system resin（1’）And thermoplastic Property elastomer（2’）Resin combination（Y）The ethene-alpha-olefin copolymer is not contained, even if or containing again smaller than 10 mass Part, therefore and aforementioned resin（X）And differ.Aforementioned resin（Y）Containing relative to polypropylene-based resin （1’）When 100 mass parts are the ethene-alpha-olefin copolymers more than 10 mass parts, internal layer adhesion is susceptible to, therefore, it is difficult to As liquid package container.Therefore, even if resin combination（Y）During containing the ethene-alpha-olefin copolymer, its content relative to The polypropylene-based resin of 100 mass parts（1’）Below preferably 5 mass parts, below more preferably 3 mass parts, more preferably Below 1 mass parts.

As polypropylene-based resin（1’）, with aforementioned resin（X）In polypropylene-based resin（1）Explanation it is same Ground explanation.

Wherein, polypropylene-based resin（1’）The construction unit from propylene monomer content be preferably more than 80mol%, More preferably 80 ~ 100mol%, more preferably 80 ~ 99mol%, particularly preferably 85 ~ 95mol%.

In addition, polypropylene-based resin（1’）Fusing point be preferably 120 ~ 140 DEG C.By making polypropylene-based resin（1’）It is molten Point is more than 120 DEG C, easily suppresses internal layer adhesion.In addition, by making polypropylene-based resin（1’）Fusing point be less than 140 DEG C, Heat sealability becomes good.

In addition, as polypropylene-based resin（1’）, it is preferably selected from Propylene-ethylene random copolymer, Propylene-ethylene block Copolymer, propene-1-butene random copolymer, propylene-ethylene-butene random copolymer, propylene pentene-1 random copolymer, propylene- Hexene random copolymer, propylene-octene random copolymer, propylene-ethylene-pentene random copolymer and propylene-ethylene-hexene without At least a kind in rule copolymer.

In addition, thermoplastic elastomer (TPE)（2’）It is with using the construction unit from aromatic vinyl compound as main body Polymer blocks and using the construction unit from conjugated diene compound as the thermoplastic elastomer (TPE) of the polymer blocks of main body, Preferably will be with polymer blocks（A）And polymer blocks（B）Block copolymer hydrogenation obtained from thermoplastic elastomer (TPE), The polymer blocks（A）Using the construction unit from aromatic vinyl compound as main body and number-average molecular weight as 2,500 ~ 100000, the polymer blocks（B）Using the construction unit from conjugated diene compound as main body, vinyl bonding structure The content of unit is more than 50mol% and number-average molecular weight is 10000 ~ 300000, aforementioned polymer block（B）The carbon-to-carbon having More than the 80mol% of double bond is hydrogenated with, and the number-average molecular weight of the thermoplastic elastomer (TPE) is preferably 20000 ~ 500000.

For will be with polymer blocks（A）And polymer blocks（B）Block copolymer hydrogenation obtained from thermoplasticity Elastomer, with aforementioned thermoplastic's elastomer（2）Explanation similarly illustrate, preferred embodiment is also identical, and manufacture method is also same Sample ground explanation.

（The content of each composition）

Resin combination（Y）Contain polypropylene-based resin（1’）（Hereinafter referred to as composition（1’））100 mass parts and thermoplasticity Elastomer（2’）（Hereinafter referred to as composition（2’））5 ~ 250 mass parts.Composition（2’）Content be less than 5 mass parts when, flexibility drop Low, during more than 250 mass parts, inner face adhesion becomes obvious and molding processibility variation, therefore less economical.From identical viewpoint Set out, resin combination（Y）Preferably comprise composition（1’）100 mass parts and composition（2’）10 ~ 150 mass parts, further preferably Composition（1’）100 mass parts and composition（2’）20 ~ 100 mass parts, further preferably composition（1’）100 mass parts and composition （2’）20 ~ 60 mass parts, particularly preferably contain composition（1’）100 mass parts and composition（2’）35 ~ 60 mass parts.

Resin combination（Y）In, when the content of each composition is in above range, the transparency, heat sealability and heat resistance become Well, internal layer adhesion is also easily suppressed.

Aforementioned resin（Y）In, except aforesaid ingredients（1’）With（2’）In addition, the model of effect of the present invention is not being damaged In enclosing, the additives such as antioxidant, ultra-violet absorber, light stabilizer, colouring agent, crystallization nucleating agent can also be contained；Hydrogenation The hydrogenation such as chroman indene resin, hydrogenated rosin system resin, hydrogenated terpene resin, alicyclic ring family hydrogenated petroleum resin is resin；By The resin of tackification such as the fatty family resin that alkene and diene polymer are formed；Hydrogenated polyisoprene, hydrogenated butadiene polymer, hydrogen Change styrene butadiene random copolymer, hydrogenated styrene isoprene random copolymer, butyl rubber, polyisobutene, poly- Other polymer such as butylene.

It should be noted that from from the viewpoint of effect of the present invention, resin combination（Y）In aforesaid ingredients（1’）With （2’）Total content be preferably more than 50 mass %, more preferably more than 70 mass %, more preferably more than 80 mass %, more preferably It is more than 90 mass %, more preferably more than 95 mass %.

（Outer layer）

Illustrated with the material that the layer of atmosphere is outer layer when then, for use as liquid package container.Outer layer By following resin combinations（Z）Composition.

Resin combination（Z）：Polypropylene-based resin containing 100 mass parts（1’’）With the thermoplastic elastomehc of 0 ~ 35 mass parts Gonosome（2’’）Resin combination, the polypropylene-based resin（1’’）In be derived from the content of construction unit of propylene monomer and be More than 60mol%, thermoplastic elastomer (TPE)（2’’）With gathering using the construction unit from aromatic vinyl compound as main body Compound block and using the construction unit from conjugated diene compound as the polymer blocks of main body.

Polypropylene-based resin（1’’）With aforementioned resin（X）In polypropylene-based resin（1）Explanation similarly say It is bright.

Wherein, polypropylene-based resin（1’’）Fusing point be preferably 140 ~ 180 DEG C, more preferably 150 ~ 170 DEG C, further Preferably 155 ~ 170 DEG C.

In addition, as polypropylene-based resin（1’’）, be preferably selected from HOPP, Propylene-ethylene random copolymer, Propylene-ethylene block copolymer, propene-1-butene random copolymer, propylene-ethylene-butene random copolymer, propylene pentene-1 without Rule copolymer, propylene-hexene random copolymer, propylene-octene random copolymer, propylene-ethylene-pentene random copolymer and third At least a kind in alkene-polyethylene-hexene random copolymer.Wherein, it is excellent from less expensive and from the viewpoint of can easily obtaining Elect HOPP, Propylene-ethylene random copolymer, propylene-ethylene block copolymer, more preferably HOPP, third as Alkene-ethylene atactic copolymer, more preferably HOPP.

In addition, thermoplastic elastomer (TPE)（2’’）It is with using the construction unit from aromatic vinyl compound as main body Polymer blocks and using the construction unit from conjugated diene compound as the thermoplastic elastic of the polymer blocks of main body Body, preferably will be with polymer blocks（A）And polymer blocks（B）Block copolymer hydrogenation obtained from thermoplastic elastic Body, the polymer blocks（A）So that the construction unit from aromatic vinyl compound is as main body and number-average molecular weight is 2, 500 ~ 100000, the polymer blocks（B）It is bonded as main body, vinyl using the construction unit from conjugated diene compound The content of construction unit is more than 50mol% and number-average molecular weight is 10000 ~ 300000, aforementioned polymer block（B）Have More than the 80mol% of carbon-to-carbon double bond is hydrogenated with, and the number-average molecular weight of the thermoplastic elastomer (TPE) be preferably 20000 ~ 500000。

（The content of each composition）

Resin combination（Z）Contain polypropylene-based resin（1’’）（Hereinafter referred to as composition（1’’））100 mass parts and thermoplastic Property elastomer（2’’）（Hereinafter referred to as composition（2’’））0 ~ 35 mass parts.Composition（2’’）Content relative to composition（1’’）100 When mass parts are more than 35 mass parts, molding processibility is deteriorated, therefore less economical.In addition, composition（2’’）Content relative into Point（1’’）When 100 mass parts are below 35 mass parts, composition（1’’）Content ratio become abundant, make liquid package container Shi Rongyi cuts into the size of bag, heat resistance and high mechanical strength and adherence step-down, also excellent therefore, it is possible to obtain treatability Liquid package container.

From from the viewpoint of above-mentioned, composition（2’’）Composition of the content relative to 100 mass parts（1’’）Preferably 0 ~ 30 Mass parts, more preferably 0 ~ 15 mass parts, more preferably 0 ~ 8 mass parts.

Resin combination（Z）In, except aforesaid ingredients（1’’）With（2’’）In addition, the scope of effect of the present invention is not being damaged It is interior, the additives such as antioxidant, ultra-violet absorber, light stabilizer, colouring agent, crystallization nucleating agent can also be contained；Hydrogenation color The hydrogenations such as full indene resin, hydrogenated rosin system resin, hydrogenated terpene resin, alicyclic ring family hydrogenated petroleum resin are resin；By alkene The resin of tackification such as the fatty family resin that hydrocarbon and diene polymer are formed；Hydrogenated polyisoprene, hydrogenated butadiene polymer, hydrogenation Styrene butadiene random copolymer, hydrogenated styrene isoprene random copolymer, butyl rubber, polyisobutene, poly- fourth Other polymer such as alkene.In addition, resin combination（Z）Content containing the construction unit from vinyl monomer is 50 ~ 95mol% Ethene-alpha-olefin copolymer when, composition of its content relative to 100 mass parts（1’’）Preferably smaller than 10 mass parts.

It should be noted that from from the viewpoint of effect of the present invention, resin combination（Z）In aforesaid ingredients（1’’）With （2’’）Total content be preferably more than 50 mass %, more preferably more than 70 mass %, more preferably more than 80 mass %, more preferably It is more than 90 mass %, more preferably more than 95 mass %.

（The thickness of internal layer, intermediate layer and outer layer）

The thickness of foregoing internal layer, intermediate layer and outer layer is not particularly limited, and can suitably be adjusted according to purposes.Internal layer Thickness is preferably 5 ~ 30 μm, more preferably 10 ~ 30 μm.The thickness in intermediate layer is preferably 100 ~ 300 μm, more preferably 100 ~ 200 μ M, more preferably 100 ~ 180 μm.The thickness of outer layer is preferably 15 ~ 120 μm, is more preferably 15 ~ 80 μm, is more preferably 15~70μm。

Do not damaging in the range of effect of the present invention, foregoing internal layer, intermediate layer, the interlayer of outer layer, the surface of outer layer may be used also With with other layers.As other layers, adhesive linkage, protective layer, coat, reflection layer, light absorbing zone etc. can be included.

Used as liquid package container of the invention, preferably foregoing internal layer is contacted with foregoing intermediate layer, preferably Foregoing intermediate layer is contacted with foregoing outer layer.

[manufacture method of liquid package container]

The liquid package container constituted as the layered product by least 3 layers with foregoing internal layer, intermediate layer and outer layer Manufacture method, is not particularly limited, and layered product is formed using the manufacture method of known layered product, is then sealed, so After cut off（Cut）And liquid package container is made, sterilization treatment is further carried out in the case of medical application.Herein, Using abovementioned layers resin combination when, film mouldability becomes good, thus with easily formed without flake and foreign matter etc. Film（Layered product）This advantage.

As the manufacture method of layered product, for example following method is preferably included.First, using single axle extruding machine, The kneading machines such as biaxial extruder, kneader, Banbury mixer, roller are kneaded to the material of each layer, so as to prepare each layer Resin combination.By each resin combination of gained by using multilayer T moulds co-extrusion modling, used multi-layer circular T moulds air cooling or water-cooled inflation shaping etc. and be shaped to membranaceous, sheet or tubulose etc..Resin temperature during shaping is preferably 150 ~ 300 DEG C, more preferably 180 ~ 250 DEG C, more preferably 180 ~ 220 DEG C.Cooling when air cooling or water-cooled inflation are molded Temperature is preferably 7 ~ 70 DEG C, more preferably 10 ~ 40 DEG C.In addition, from from the viewpoint of the ease of manufacturing of liquid package container, it is excellent Choosing is shaped to tubulose.If the formed body of tubulose, then by cutting off after heat-sealing（Cut out）And liquid package container can be manufactured. On the other hand, be membranaceous or during sheet formed body, it is necessary to 2 are overlapped and are sealed.

In the case of medical application, sterilization treatment is further used as, carries out water vapour sterilizing, autoclave sterilizing etc.. In the case that autoclave sterilizes, heating-up temperature is preferably 100 ~ 150 DEG C, more preferably 110 ~ 140 DEG C.

It should be noted that effectively serving as the medical containers such as infusion bag by possessing lid etc., the lid includes For injecting the hole of liquid, the glue bolt for taking out liquid.Like this, the present invention is also provided and possesses aforementioned liquids packing container Medical container.

[purposes]

Liquid package container of the invention can be used for various uses.For example, in addition to foregoing medical container, also effectively Food container as packaging distillation food, mayonnaise, catsup, cold drink, ice cream etc. etc..

Embodiment

Hereinafter, the present invention is illustrated by embodiment etc., but the present invention is not limited to these embodiments completely.Need Illustrate, each physical property in embodiment and comparative example is determined or evaluated by following method.

[determining or evaluation method]

The number-average molecular weights of ＜ 1.（Mn）And molecular weight distribution（Mw/Mn）＞

Chromatogram is impregnated with by gel（GPC）Obtained in the form of polystyrene standard conversion molecular weight.

Device：GPC devices " HLC-8020 "（TOSOH Co., Ltd's system）

Splitter：" TSKgelGMHXL ", " G4000HXL " and " G5000HXL " series connection of TOSOH Co., Ltd's manufacture connects Knot.

Eluant, eluent：Tetrahydrofuran

Eluant, eluent flow：1.0ml/ minutes

Column temperature：40℃

Detection method：Differential refraction rate（RI）.

（1-1. polymer blocks（A）Mn and polymer blocks（B）Mn assay method）

In each Production Example, for the Mn of each polymer blocks, it is sampled in the stage for foring each polymer blocks, is pressed Mn is determined according to the above method.Specifically, polymer blocks are formed by the polymerization of styrene（A）When, carry out Mn's first Determine, then further make butadiene and/or isoprene polymerization, so as to form polymer blocks（B）When, carry out polymer embedding Section（A）-（B）Mn measure.Now, the Mn of the latter is polymer blocks（A）With（B）Overall Mn, therefore before subtracting The polymer blocks of measure（A）Mn, so as to calculate polymer blocks（B）Mn.Form polymer blocks（A）-（B）-（A）'s In the case of, the polymer blocks for eventually forming are calculated with identical method（A）, forming polymer blocks（A）-（B）-（A）- （B）In the case of, the polymer blocks for eventually forming are calculated with identical method（B）.

Polymer blocks in the thermoplastic elastomer (TPE)s of ＜ 2.（A）Content, polymer blocks（B）Vinyl bonds resultant （1,2- bonded amounts and 3,4- bonded amounts）＞

Pass through¹H-NMR determines to obtain.

Device：Nuclear magnetic resonance device " Lambda-500 "（Jeol Ltd.'s system）

Solvent：Deuterochloroform.

The fusing point ＞ of ＜ 3.

Use differential scanning calorimetry (DSC)（DSC）“TGA/DSC1StarSystem”（MettlerToledo company systems）, will be with 10 DEG C/min of programming rate be heated to 250 DEG C from 30 DEG C and make its melt sample with 10 DEG C/min of cooling rate from After 250 DEG C are cooled to 30 DEG C, the endothermic peak that will be determined when being warming up to 250 DEG C from 30 DEG C again with 10 DEG C/min of programming rate Summit temperature as fusing point.

Using the layered product of 200 μm of the thickness manufactured in each embodiment and comparative example, each survey is carried out as follows Fixed and evaluation.

＜ I. Young's modulus ＞

Manufactured size is the test film of 25mm × 75mm, is used " イ Application ストロ Application 3345 "（イ Application ストロ Application company System）, Young's modulus was determined under conditions of 5mm/ minutes.The smaller then flexibility of value is more excellent.Desired value is below 300MPa.

Mist degree ＞ after ＜ II. mist degrees, sterilization treatment

Use haze meter " HR-100 "（Murakami K. K.'s dye technology research is made）Determine mist degree.

In addition, by layered product autoclave with 121 DEG C of sterilization treatments 30 minutes after, operate to determine mist as described above Degree.

The smaller then transparency of value is more excellent.Desired value is less than 20% if before sterilization treatment, if after sterilization treatment Desired value is less than 30%.

＜ III. heat seal strengths ＞

In the state of the internal layer for making layered product contacts with each other, heat is carried out under conditions of 140 DEG C, 0.4MPa and 1 second Envelope, makes test film.Using the test film, with " イ Application ストロ Application 3345 "（イ Application ストロ Application company systems）At 300mm/ minutes Under conditions of carry out 180 ° of disbonded tests.Value is more big then to represent that heat seal strength is higher.Preferably more than 70N/25mm.

＜ IV. broken bag intensity（Normal temperature）＞

Layered product is cut into the size of 15cm × 9cm, using 2 laminates, internal layer is coincided with one another, by 4 in 3 while In 140 DEG C, 0.4MPa and after being sealed under conditions of 1 second heat time, enter the water of 100cc from 1 marginal not of opening, then 1 side is sealed with above-mentioned identical condition, so as to make the liquid package container that inner capacities is 100cc.

After gained liquid package container is stood on iron plate in the environment of 23 DEG C, make 1kg（9.8N）Iron plate from upper Side falls 3 times.Identical measure is carried out with the interval of 3cm, the limit level that bag is not ruptured is used as the broken bag intensity under normal temperature Index.Value is more big then to represent that the broken bag intensity under normal temperature is higher.Preferably more than 40cm, more preferably more than 45cm, especially Preferably more than 48cm.

In addition, after the experiment of the broken bag intensity, using scanning electron microscope（SEM）Observation liquid package container, sees The cracking carried out from the heat-seal land of internal layer and the boundary line of non-heat-seal land is examined, is evaluated according to following metewands.

A：Cracking is abreast carried out along the interface in internal layer-intermediate layer with the face direction of layered product（Cracking ways of carrying out A）.

B：Cracking is carried out towards layered product surface（Cracking ways of carrying out B）.

＜ V. low temperature broken bag intensity ＞

The liquid package container made in the evaluation of above-mentioned broken bag intensity is rested on iron plate in the environment of 4 DEG C, so After make 1kg（9.8N）Iron plate from top fall 3 times.Identical measure is carried out with the interval of 3cm, the upper limit for height that bag is not ruptured Spend as the index of low temperature broken bag intensity.Value is more big then to represent that low temperature broken bag intensity is higher.Preferably more than 20cm, more preferably More than 23cm, more preferably more than 25cm, particularly preferably more than 28cm.

＜ VI. internal layers adhesion ＞

With 0.2kg/cm²Pressure the internal layer of layered product is contacted with each other in the state of, on 120 DEG C of hot plate stand 5 seconds.The internal layer of layered product is peeled off with hand each other, is evaluated according to following metewands.

1：There is no peel resistance, can be easily peeled off.

2：There is peel resistance, with the deformation of layered product, albefaction.

3：Peel resistance is strong, it is difficult to peel off.

＜ VII. film mouldabilities ＞

Confirm layered product（Film）Fluctuation（surging）（Extrusion capacity in processing and forming is non-constant, the shape of product, chi It is very little to become irregular, or regular fluctuation）And whether there is foreign matter and flake because mixing is bad, according to following evaluation bases Standard is evaluated, as the index of film mouldability.

A：The MD directions of the film of 2m, the thickness and precision in TD directions are cut out along MD directions and is respectively less than ± 10%, and visually confirmed Less than foreign matter and flake.

B：Cut out along MD directions the thickness and precision at least one of MD directions, the TD directions of the film of 2m direction for ± More than 10%, or visually it is able to confirm that foreign matter or flake.

[raw polymer used in embodiment]

The details or manufacture method of each composition used in embodiment described below and comparative example.In addition, table 1 ~ 3 is summed up The physics value of each composition.

(polypropylene-based resin)

PP1：“PT-100”（LCY CHEMICAL company systems）, HOPP, MFR1.6g/10 minutes（230℃、 21.6N）, 164 DEG C of fusing point, propylene content 100mol%

PP2：“SB-520Y”（LOTTE CHEMICAL company systems）, Propylene-ethylene random copolymer, MFR2.4g/10 point Clock（230℃、21.6N）, 154 DEG C of fusing point, propylene content 97mol%

PP3：“SFC-750D“（LOTTE CHEMICAL company systems）, propene-1-butene random copolymer, MFR5.8g/10 point Clock（230℃、21.6N）, 130 DEG C of fusing point, propylene content 90mol%

[table 1]

。

(thermoplastic elastomer (TPE)（Hydrogenation thing）〕

TPS1：Styrene-（Isoprene/butadiene）The hydrogenation thing of-styrene block copolymer, vinyl bonds resultant 60%

TPS2：The hydrogenation thing of SIS, vinyl bonds resultant 55%

TPS3：The hydrogenation thing of SBS, vinyl bonds resultant 75%

TPS4：Styrene-（Isoprene/butadiene）The hydrogenation thing of-styrene block copolymer, vinyl bonds resultant 60%

TPS5：Styrene-（Isoprene/butadiene）The hydrogenation thing of-styrene block copolymer, vinyl bonds resultant 60%

TPS6：Styrene-（Isoprene/butadiene）The hydrogenation thing of-styrene block copolymer, vinyl bonds resultant 60%

TPS7：Styrene-（Isoprene/butadiene）The hydrogenation thing of-styrene block copolymer, vinyl bonds resultant 80%

TPS8：Styrene-（Isoprene/butadiene）The hydrogenation thing of-styrene block copolymer, vinyl bonds resultant 60%

TPS9：Styrene-（Isoprene/butadiene）The hydrogenation thing of-styrene block copolymer, vinyl bonds resultant 70%

TPS10：The hydrogenation thing of s-B-S-butadiene block copolymer, vinyl bonds resultant 75%

TPS11：Styrene-（Isoprene/butadiene）The hydrogenation thing of-styrene block copolymer, vinyl bonds resultant 60%

TPS12：The hydrogenation thing of SIS, vinyl bonds resultant 7%

TPS13：The hydrogenation thing of SBS, vinyl bonds resultant 40%

The manufacture method of TPS1 ~ TPS13 is as follows.

[Production Example 1]

In nitrogen displacement and dry pressure vessel has been carried out, input is as the hexamethylene 50.0kg of solvent, as cloudy The s-butyl lithium of cation polymerization initiator（The cyclohexane solution of 10.5 mass %）76g（S-butyl lithium 8.0g）, put into as Louis The tetrahydrofuran 313g of this alkali.After being warming up to 50 DEG C, styrene is added（1）0.5kg and make its polymerization 1 hour, then add different The mixed liquor of pentadiene 8.2kg and butadiene 6.5kg, be polymerized within 2 hours, and then add styrene（2）1.5kg and be polymerized 1 Hour, so as to obtain comprising polystyrene-poly（Isoprene/butadiene）The reaction solution of-polystyrene triblock copolymer. In the reaction solution, added as hydrogenation catalyst relative to the palladium carbon that aforesaid block copolymer is 5 mass %（Palladium load capacity：5 Quality %）, the reaction of 10 hours is carried out under conditions of Hydrogen Vapor Pressure 2MPa, 150 DEG C.After letting cool and bleeding off pressure, gone by filtering Except palladium carbon, filtrate is concentrated, and then be vacuum dried, so as to obtain polystyrene-poly（Isoprene/butadiene）- polyphenyl second The hydrogenation thing of alkene triblock copolymer（Hereinafter referred to as hydrogenated block copolymer TPS1）.For hydrogenated block copolymer（TPS1）Enter The above-mentioned evaluation of row.It should be noted that carrying out the measure of the Mn of each polymer blocks according to preceding method.Show the result in table 2.

[Production Example 2,4 ~ 9 and Production Example 13]

In addition to the cooperation being changed to described in table 2, it is same with Production Example 1 operation and manufacture hydrogenated block copolymer （TPS2）、（TPS4）~（TPS9）With（TPS13）.For gained hydrogenated block copolymer（TPS2）、（TPS4）~（TPS9）With （TPS13）Carry out above-mentioned evaluation.It should be noted that carrying out the measure of the Mn of each polymer blocks according to preceding method.Will knot Fruit is shown in table 2.

[Production Example 3]

N, N, N are used as lewis base ', N '-tetramethylethylenediamine is altered to the cooperation described in table 2, except this it Outward, operation same with Production Example 1, so as to manufacture hydrogenated block copolymer（TPS3）.For gained hydrogenated block copolymer （TPS3）, carry out above-mentioned evaluation.It should be noted that carrying out the measure of the Mn of each polymer blocks according to preceding method.Will knot Fruit is shown in table 2.

[Production Example 10]

N, N, N are used as lewis base ', N '-tetramethylethylenediamine, according to the cooperation described in table 2, adds styrene （1）And be polymerized 1 hour, then add butadiene（1）And be polymerized within 2 hours, further add styrene（2）And polymerization 1 is small When, further add butadiene（2）And be polymerized 1 hour, in addition, operation same with Production Example 1, so as to manufacture hydrogenated diblock Copolymer（TPS10）.For gained hydrogenated block copolymer（TPS10）, carry out above-mentioned evaluation.It should be noted that according to preceding The method of stating carries out the measure of the Mn of each polymer blocks.Show the result in table 2.

[Production Example 11]

According to the cooperation described in table 2, styrene is polymerized, after then carrying out the polymerization of butadiene, as coupling agent And methyl benzoate 100g is added, with 60 DEG C react within 1 hour, in addition, operation same with Production Example 1, so as to manufacture Hydrogenated block copolymer（TPS11）.For gained hydrogenated block copolymer（TPS11）, carry out above-mentioned evaluation.Need explanation It is that the measure of the Mn of each polymer blocks is carried out according to preceding method.Show the result in table 2.

[Production Example 12]

Without the tetrahydrofuran as lewis base, the cooperation described in table 2 is altered to, it is in addition, same with Production Example 1 Sample is operated, so as to manufacture hydrogenated block copolymer（TPS12）.For gained hydrogenated block copolymer（TPS12）, carry out commentary Valency.Show the result in table 2.

[table 2]

。

(ethene-alpha-olefin copolymer, poly alpha olefin)

POE1：“タフマーP-0775”（Mitsui Chemicals, Inc's system）, ethylene-propylene random copolymer, MFR0.6g/10 minutes（230℃、21.6N）, 43 DEG C of fusing point, ethylene contents 56mol%

POE2：Ethylene/Butylene random copolymer, " タフマー A-4050S "（Mitsui Chemicals, Inc's system）、 MFR6.7g/10 minutes（230℃、21.6N）, 47 DEG C of fusing point, ethylene contents 80mol%

POE3：“エンゲージ8200”（Dow Chemical company systems）, ethylene-octene random copolymer, MFR5g/ 10 minutes（190℃、21.6N）, 65 DEG C of fusing point, ethylene contents 93mol%

POE4：“タフマーP-0275”（Mitsui Chemicals, Inc's system）, ethylene-propylene random copolymer, MFR5.4g/10 minutes（230℃、21.6N）, 49 DEG C of fusing point, ethylene contents 71mol%

POE5：“VISTAMAXX6102”（Exxon Mobile company systems）, Propylene-ethylene random copolymer, MFR3g/10 Minute（230℃、21.6N）, 108 DEG C of fusing point, ethylene contents 12mol%

POE6：“タフマーBL-2000”（Mitsui Chemicals, Inc's system）, homopolymerization polybutene, MFR=0.2g/10 minutes （190℃、21.6N）, 123 DEG C of fusing point, ethylene contents 0mol%

[table 3]

。

[embodiment 1 ~ 20, comparative example 1 ~ 11：The manufacture of layered product]

Use the material described in foregoing table 1 ~ 3, the material and the material of outer layer of material, intermediate layer for internal layer Material, respectively according to the mixing ratio shown in table 4 below or table 5, using under water-cooled to inflation forming machine, in resin temperature 200 DEG C, 20 DEG C of cooling water temperature, under conditions of linear velocity 10m/ minutes, be shaped to the layered product of 200 μm of thickness（Film）.On each layer Thickness, for embodiment 1 ~ 14,16 ~ 20 and comparative example 1 ~ 11, be set to 20 μm of internal layer, 130 μm of intermediate layer, 50 μm of outer layer, pin To embodiment 15,20 μm of internal layer, 160 μm of intermediate layer, 20 μm of outer layer are set to.For the physical property of each layered product of gained, the He of table 4 is shown in Table 5.

And then, in embodiment 1 and comparative example 1, scanning electron microscope during cracking ways of carrying out will be observed（SEM）According to Piece is shown in Fig. 2 and Fig. 3.

[table 4]

。

[table 5]

。

Intermediate layer is not used composition（3）Or composition（3）Poor comparative example 1 and 2 in, cracking carried out according to cracking Mode B and carry out, normal temperature（23℃）Under broken bag low intensity.Internal layer has used composition（3）Comparative example 3,4 and 9（Comparative example 3 Internal layer with 4 has used resin combination（X）.）There is the problem of internal layer adhesion, especially the flexibility of comparative example 9 and transparent Property is also deteriorated.Intermediate layer is not using meeting composition given to this invention（3）Composition（Ethylene contents are few）The He of comparative example 5 In 6, cracking is carried out because of cracking ways of carrying out B, normal temperature（23℃）Under broken bag low intensity.Intermediate layer is not used composition（2）'s Composition in comparative example 7, intermediate layer（3）Content more than comparative example 8, intermediate layer using do not meet it is given to this invention into Point（2）Composition（Vinyl bonds resultant is few.）Comparative example 10 and 11 in, it is any in the case of flexibility, low temperature（4℃）Under Broken bag intensity and the transparency are reduced.

On the other hand, only intermediate layer has used resin combination（X）Embodiment 1 ~ 20 in, it is any in the case of can obtain Must have good flexibility, the transparency, high heat-sealing strength, normal temperature（23℃）Under broken bag intensity high, low temperature（4℃）Under height The layered product of broken bag intensity and low internal layer adherence.Especially it is believed that：Broken bag intensity at 23 DEG C and 4 DEG C is obviously improved and is Because in any embodiment, cracking is carried out with being cracked ways of carrying out A.

It should be noted that for prepared the film mouldability evaluated, the resin combination in the intermediate layer of embodiment 8 The molecular weight of the TPS5 that thing is used is higher, therefore shows excellent result at aspects such as broken bag intensity, on the other hand, utilizes This processing conditions confirm fluctuation and foreign matter, but the layered product of other embodiments film good forming ability.

Industry applications

Liquid package container of the invention can be used for various uses.For example, in addition to foregoing medical container, can also have Effect ground is used as food container of packaging distillation food, mayonnaise, catsup, cold drink, ice cream etc. etc..

Claims

1. liquid package container, it is made up of at least 3 layers with internal layer, intermediate layer and outer layer of layered product, the internal layer by Following resin combination Y compositions, the outer layer is made up of following resin combination Z, and the intermediate layer is by following resin combination X Composition,

Resin combination X：The thermoplastic elastomer (TPE) 2 and 10 ~ 95 of polypropylene-based resin 1,5 ~ 95 mass parts containing 100 mass parts The resin combination of the ethene-alpha-olefin copolymer of mass parts, the structure list from propylene monomer in the polypropylene-based resin 1 The content of unit is more than 60mol%；The thermoplastic elastomer (TPE) 2 is by the block with polymer blocks A and polymer blocks B Thermoplastic elastomer (TPE) obtained from copolymer hydrogenating, the polymer blocks A is with the structure list from aromatic vinyl compound Unit is as main body and number-average molecular weight is 2,500 ~ 100,000, and the polymer blocks B is with the knot from conjugated diene compound Structure unit is more than 50mol% as main body, the content of vinyl bonding structure unit and number-average molecular weight is 10,000 ~ 300, 000, more than the 80mol% of the carbon-to-carbon double bond that the polymer blocks B has is hydrogenated with, the thermoplastic elastomer (TPE) 2 Number-average molecular weight is 20,000 ~ 500,000；The construction unit from vinyl monomer contains in the ethene-alpha-olefin copolymer It is 50 ~ 95mol% to measure；

Resin combination Y：The thermoplastic elastomer (TPE) 2 ' of the polypropylene-based resin 1 ' containing 100 mass parts and 5 ~ 250 mass parts Resin combination, the content of the construction unit from propylene monomer is more than 60mol% in the polypropylene-based resin 1 ', described Thermoplastic elastomer (TPE) 2 ' is with the polymer blocks and Yi Yuan using the construction unit from aromatic vinyl compound as main body The construction unit of self-conjugate diolefin compound as main body polymer blocks, wherein, do not contain the structure from vinyl monomer The content of unit is the ethene-alpha-olefin copolymer of 50 ~ 95mol%, even if or containing again smaller than 10 mass parts；

Resin combination Z：Polypropylene-based resin 1 ' containing the 100 mass parts thermoplastic elastomer (TPE) 2 ' of 0 ~ 35 mass parts ' and ' Resin combination, the polypropylene-based resin 1 ' ' in be derived from propylene monomer construction unit content be more than 60mol%, it is described Thermoplastic elastomer (TPE) 2 ' ' with the polymer blocks and Yi Yuan using the construction unit from aromatic vinyl compound as main body The construction unit of self-conjugate diolefin compound as main body polymer blocks.

2. liquid package container as claimed in claim 1, wherein, the ethene-alpha-olefin copolymer is in 230 DEG C, load Melt flow rate (MFR) under conditions of 21.6N is 0.1 ~ 30g/10 minutes, and fusing point is 40 ~ 120 DEG C.

3. liquid package container as claimed in claim 1 or 2, wherein, the polypropylene-based resin 1,1 ' and 1 ' ' is each independent Ground is selected from HOPP, Propylene-ethylene random copolymer, propylene-ethylene block copolymer, propene-1-butene random copolymerization Thing, propylene-ethylene-butene random copolymer, propylene pentene-1 random copolymer, propylene-hexene random copolymer, propylene-octene At least a kind in random copolymer, propylene-ethylene-pentene random copolymer and propylene-ethylene-hexene random copolymer.

4. liquid package container as claimed in claim 1 or 2, wherein, the fusing point of the polypropylene-based resin 1 ' is 120 ~ 140 ℃。

5. liquid package container as claimed in claim 1 or 2, wherein, the polypropylene-based resin 1 ' ' it is HOPP.

6. liquid package container as claimed in claim 1 or 2, wherein, the thermoplastic elastomer (TPE) 2 ' and 2 ' ' is independently of one another It is by with thermoplastic elastomer (TPE), the polymerization obtained from the block copolymer of polymer blocks A and polymer blocks B hydrogenation Thing block A is so that the construction unit from aromatic vinyl compound is as main body and number-average molecular weight is 2,500 ~ 100,000, institute Polymer blocks B is stated using the construction unit from conjugated diene compound as main body, the content of vinyl bonding structure unit For more than 50mol% and number-average molecular weight are 10,000 ~ 300,000, the carbon-to-carbon double bond having in the polymer blocks B More than 80mol% is hydrogenated with, and the number-average molecular weight of the thermoplastic elastomer (TPE) is 20,000 ~ 500,000.

7. liquid package container as claimed in claim 1 or 2, wherein, the thickness of each layer is in 5 ~ 30 μm of internal layer, middle Layer 100 ~ 300 μm, the scope of 15 ~ 120 μm of outer layer.

8. medical container, it has the liquid package container any one of claim 1 ~ 7.